CN104752759B - Preparation method of crystalline state Li-Sn-S series inorganic lithium ion solid electrolyte - Google Patents

Preparation method of crystalline state Li-Sn-S series inorganic lithium ion solid electrolyte Download PDF

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Publication number
CN104752759B
CN104752759B CN201510197400.0A CN201510197400A CN104752759B CN 104752759 B CN104752759 B CN 104752759B CN 201510197400 A CN201510197400 A CN 201510197400A CN 104752759 B CN104752759 B CN 104752759B
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solid electrolyte
lithium ion
crystalline state
water
inorganic lithium
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CN104752759A (en
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韦伟峰
曾小慧
丁正平
柳佳图
陈立宝
张大同
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Guangdong Jusheng Technology Co.,Ltd.
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method of a crystalline state Li-Sn-S series inorganic lithium ion solid electrolyte. The method comprises the following steps: introducing H2S gas or adding a water-soluble sulfide into a LiOH.H2O aqueous solution in an enclosed container, reacting for a certain time period, and adding an aqueous solution containing a metal Sn element; introducing protective gas for reacting continually, adding an organic reagent, putting the mixture into a low-temperature environment, drying a crystal which is separated out, and removing crystalized water by means of thermal treatment to obtain a product. An all-solid electrolyte is prepared by adopting a novel wet process. Compared with the conventional solid-phase synthesis, the method has the remarkable advantages of short reaction time and controllability of the product morphology.

Description

Crystalline state li-sn-s system inorganic lithium ion solid electrolyte preparation method
Technical field
The present invention relates to a kind of all-solid-state lithium-ion battery method for preparing solid electrolyte, particularly to a kind of crystallization State li-sn-s system inorganic lithium ion solid electrolyte preparation method.
Background technology
, there is leakage in the organic electrolyte that lithium ion battery uses in the market, corrosion electrode even occurs oxidation combustion The safety issues such as burning.Lithium ion inorganic solid electrolyte can be very good to avoid the problems referred to above, and has lithium ion conducting rate Height (reaches as high as 10-2S/cm), chemical stability is good, potential window big (5～10v) the advantages of, and can be with high-energy-density Energy storage material sulfur electrode coordinates, pole be hopeful to develop high-energy-density, safety, can applied at elevated temperature new type lithium ion battery.li- The inorganic lithium ion solid electrolyte of sn-s system is a kind of electrolyte studying more at present, such as applicant Toyota automatic vehicle Co., Ltd. has been disclosed this electrolyte in patent application 201380007092x.But prepare this material at present Method is solid phase synthesis process, such as also discloses that this preparation method in above-mentioned patent application.
Content of the invention
The present invention is intended to provide a kind of wet processing method being different from solid-phase synthesis completely is preparing li-sn-s system no Machine lithium ion solid electrolyte material.The present invention is realized by below scheme:
The first step: to there being lioh h2First it is passed through h in the hermetic container of o aqueous solution2S gas or the water-soluble sulfur of addition After compound reaction certain time, then the compound water solution being added thereto to containing sn element carries out reaction and is completely dissolved to precipitation； Wherein the mol ratio of li:s:sn is 8:1:(4～6)
Second step: under the conditions of solution alkaline, in 40～80 DEG C, be passed through guarantor in the product obtaining to after first step reaction Shield gas continues reaction certain time or makes the reaction of the first step continue to react certain time under the conditions of fully sealing；Again to it Middle addition can be miscible with water organic reagent such as acetone, ethanol, methanol etc., be placed in afterwards in low temperature environment, until separate out crystal； Described protective gas is selected from least one of nitrogen or noble gases.
3rd step: second step separate out crystal after drying, then at 300 DEG C less than crystal decomposition temperature below Held for some time in temperature environment, obtains product.
Test finds, at least one that the sulfide in the first step is selected from alkali metal sulphide or ammonium sulfide is more excellent.
For shortening the crystallize time, not higher than 0 DEG C of the temperature of the low temperature environment of second step.
For reducing impurity, precipitation crystal organic solvent such as acetone, ethanol, methanol etc. that first warp can be miscible with water of second step Re-dry after washing,.
The present invention prepares all solid state electrolyte using novel wet processing, compared to the remarkable advantage of conventional solid synthesis That the response time is short, controlling reaction temperature can be led to, time and select different organic reagents and control product morphology.
Specific embodiment
Embodiment 1
A kind of inorganic solid electrolyte li4sns4Preparation method as follows:
In there-necked flask, by 5.0350g (120mmol) lioh h2O stirring is dissolved in water, is passed through h thereto2S gas, Speed is 10ml/min, after being passed through 25～35min, unnecessary h2S gas is absorbed with koh solution, then by 5.259g (15mmol) sncl4·5h2After o is dissolved in 10ml water, add to there-necked flask, yellow mercury oxide to be generated all dissolves.Add excessive lioh·h2O, adjusts ph between 11～12, under the conditions of being passed through nitrogen atmosphere, after 45 DEG C of reaction 8h, then adds in flask Acetone, then it is placed in 48h in 0 DEG C of environment, separate out to there being white crystal.Filter and extract precipitate, and with acetone rinsing repeatedly, will Crystal precipitate in vacuum drying 12h, obtain light gray powder, in 350 DEG C of environment insulation 12h to slough powdered product Water of crystallization, obtain inorganic solid electrolyte li of crystalline state4sns4.
Embodiment 2
In there-necked flask, by 120mmol lioh h2O stirring is dissolved in water, is added thereto to the k of 60mmol2After s, then Sncl by 15mmol4·5h2After o is dissolved in 10ml water, add to there-necked flask, yellow mercury oxide to be generated all dissolves.With Lower step is identical with embodiment 1.
Embodiment 3
In there-necked flask, by 120mmollioh h2O stirring is dissolved in water, is passed through h thereto2S gas, speed is 10ml/min, after being passed through 25～35min, unnecessary h2S gas is absorbed with koh solution, then the snbr by 15mmol4·5h2O is molten After 10ml water, add to there-necked flask, yellow mercury oxide to be generated all dissolves.Add excessive lioh h2O, adjusts ph Between 11～12, under the conditions of being passed through nitrogen atmosphere, after 80 DEG C of reaction 3h, then add ethanol in flask, then be placed in 0 DEG C 48h in environment, separates out to there being white crystal.Filter and extract precipitate, and use ethanol, rinse repeatedly, by crystal precipitate in true Sky is dried 8h, obtains light gray powder, in 320 DEG C of environment insulation 12h to slough the water of crystallization of powdered product, tied Inorganic solid electrolyte li of crystalline state4sns4.

Claims (4)

1. a kind of inorganic lithium ion solid electrolyte preparation method of crystalline state li-sn-s it is characterised in that: enter according to the following steps OK,
The first step: to there being lioh h2First it is passed through h in the hermetic container of o aqueous solution2S gas or the water-soluble sulfide of addition After reaction certain time, then the compound water solution being added thereto to containing sn element carries out reaction and is completely dissolved to precipitation；Wherein The mol ratio of li:sn:s is 8:1:(4～6)；
Second step: under the conditions of solution alkaline, in 40～80 DEG C, be passed through shielding gas in the product obtaining to after first step reaction Body continues reaction certain time or makes the reaction of the first step continue to react certain time under the conditions of fully sealing；Add thereto again After entering organic reagent that can be miscible with water, it is placed in low temperature environment, until separating out crystal；Described protective gas is selected from nitrogen or lazy At least one of property gas；
3rd step: second step separate out crystal after drying, then at 300 DEG C less than crystal decomposition temperature below temperature Held for some time in environment, obtains product.
2. the inorganic lithium ion solid electrolyte preparation method of crystalline state li-sn-s as claimed in claim 1, its feature exists In: the sulfide in the described first step is selected from least one in alkali metal sulphide or ammonium sulfide.
3. the inorganic lithium ion solid electrolyte preparation method of crystalline state li-sn-s as claimed in claim 1 or 2, its feature It is: the low temperature environment of described second step is not higher than 0 DEG C of environment for temperature.
4. the inorganic lithium ion solid electrolyte preparation method of crystalline state li-sn-s as claimed in claim 1 or 2, its feature It is: the precipitation crystal first re-dry after organic solvent washing that can be miscible with water of described second step.
CN201510197400.0A 2015-04-23 2015-04-23 Preparation method of crystalline state Li-Sn-S series inorganic lithium ion solid electrolyte Active CN104752759B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6678405B2 (en) * 2015-07-09 2020-04-08 国立大学法人東京工業大学 Lithium solid electrolyte
US10854912B2 (en) 2016-01-12 2020-12-01 Lg Chem, Ltd. Sulfide-based solid electrolyte and all-solid-state battery applied therewith
CN108336396B (en) * 2017-12-19 2021-05-07 成都大超科技有限公司 Method for preparing organic-inorganic hybrid solid electrolyte
JP7056530B2 (en) * 2018-11-28 2022-04-19 トヨタ自動車株式会社 Method for producing modified sulfide solid electrolyte
CN111834664B (en) * 2020-08-08 2022-04-29 天目湖先进储能技术研究院有限公司 Sulfide type solid electrolyte capable of being separated and recycled and application thereof
CN112002939B (en) * 2020-08-31 2021-10-15 成都新柯力化工科技有限公司 Clean preparation method of lithium battery solid electrolyte

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CN1918668A (en) * 2004-02-12 2007-02-21 出光兴产株式会社 Lithium ion conductive sulfide-based crystallized glass and method for producing same
CN102334225A (en) * 2009-02-27 2012-01-25 丰田自动车株式会社 Solid sulfide electrolyte material
JP2012199234A (en) * 2011-03-10 2012-10-18 Osaka Prefecture Univ Lithium ion battery, and negative electrode material therefor
CN102823049A (en) * 2010-03-26 2012-12-12 国立大学法人东京工业大学 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
WO2013118722A1 (en) * 2012-02-06 2013-08-15 トヨタ自動車株式会社 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1918668A (en) * 2004-02-12 2007-02-21 出光兴产株式会社 Lithium ion conductive sulfide-based crystallized glass and method for producing same
CN102334225A (en) * 2009-02-27 2012-01-25 丰田自动车株式会社 Solid sulfide electrolyte material
CN102823049A (en) * 2010-03-26 2012-12-12 国立大学法人东京工业大学 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
JP2012199234A (en) * 2011-03-10 2012-10-18 Osaka Prefecture Univ Lithium ion battery, and negative electrode material therefor
WO2013118722A1 (en) * 2012-02-06 2013-08-15 トヨタ自動車株式会社 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material

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Denomination of invention: Preparation of crystalline Li-Sn-S inorganic lithium ion solid electrolyte

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